CN106751503B - The preparation method of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems - Google Patents
The preparation method of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems Download PDFInfo
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- CN106751503B CN106751503B CN201611121723.2A CN201611121723A CN106751503B CN 106751503 B CN106751503 B CN 106751503B CN 201611121723 A CN201611121723 A CN 201611121723A CN 106751503 B CN106751503 B CN 106751503B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of preparation methods of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems, the technical problem met simultaneously, preparation process is complicated and inconvenient to use is not easy which solve the composite material rigidity of existing intermediate temperature setting prepreg and toughness, it includes the following steps: that (1) by aromatic amine curing agent and bimaleimide resin hybrid reaction, prepares curing agent；(2) phenoxy resin is dissolved in liquid epoxies, then curing agent pre-polymerization is added, cool down again be added latent curing system master batch component be uniformly mixed, prepare a kind of middle-temperature solidifying epoxy pre-dipping material resin system for having both high-modulus, high intensity and high tenacity.
Description
Technical field
The present invention relates to field of compound material, specifically a kind of high-modules carbon fibre prepreg intermediate temperature setting asphalt mixtures modified by epoxy resin
The preparation method of resin system.
Background technique
The interface of intermediate products of the prepreg as composite element, the superiority and inferiority of quality, fiber and resin matrix is viscous
Connect the performance that intensity directly affects composite material.Carbon fibre composite is under by external force, if resin matrix is rigid
Property with toughness deficiency when, resin matrix is difficult to match with the modulus of high modulus carbon fiber and fracture deformation, then resin matrix is first
Occur yield failure, cannot effectively transmit stress, limit the performance of high-modules carbon fibre performance, improve resin matrix modulus and
Toughness can effectively improve the comprehensive performance of carbon fiber resin matrix composite.Intermediate temperature setting system has forming temperature low, all
Production cost and energy consumption can be significantly reduced in the advantages that phase is short, product good stability of the dimension, improves production efficiency.
Application No. is 201310287363.3 Chinese invention patent applications to disclose a kind of tough epoxy resin solidification body
System and preparation method thereof, the invention come epoxy resin toughened, are mentioned using thermoplastic polyetherimide, polysulfones, polyether sulfone etc.
The high impact strength and fracture toughness of solidfied material, but thermoplastic need to be dissolved and can be used in a solvent.
The Chinese invention patent application of Publication No. CN102702482A discloses high-intensitive and high-modulus thermosetting property tree
Oil/fat composition is to be made up of cyanate ester monomer, bismaleimide monomer, epoxy resin, double oxazoline compounds etc., passes through
Solidfied material has higher intensity and modulus after hybrid reaction, but resin system is hot setting and curing time is longer.
A kind of preparation of aryl imide modified epoxy resin system of the U.S. Patent Publication of Patent No. US3920768
Method is mixed with to obtain the more excellent resin system of performance using aryl imide and epoxy resin, but prepared pre-
Leaching material is substantially that sticky, craftsmanship is not poor and needs hot setting.
Summary of the invention
The present invention be exactly in order to solve the composite material rigidity of existing intermediate temperature setting prepreg and toughness be not easy to meet simultaneously,
Preparation process is complicated and technical problem inconvenient to use, provides and a kind of is mentioned with bi-maleimide modified aromatic amine curing agent
The modulus and intensity of high resin matrix, the toughening of resin matrix is realized with high molecular weight phenoxy resin, and meets prepreg preparation
Technique require and high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems easy to use preparation method.
For this purpose, the present invention provides a kind of preparation method of high-modules carbon fibre intermediate temperature setting epoxy prepreg, it will
Aromatic amine curing agent is with bimaleimide resin according to (2~4): 1 molar ratio reacts 0.5h~5h at 120~160 DEG C,
Prepare curing agent.Phenoxy resin is dissolved in liquid epoxies at 120~150 DEG C, is then added
Curing agent 0.5~1.5h of pre-polymerization is stated, then is cooled to 70~80 DEG C of addition latent curing system master batch components and mixes
It closes uniformly, prepares the middle-temperature solidifying epoxy pre-dipping material resin system of activeness and quietness.Above-mentioned resin system is applied using adhesive film machine
Film, it is then compound via compounding machine and reinforcing fiber or fabric, preparation heat resistance in the good synchronous activeness and quietness of craftsmanship
Temperature solidification prepreg.The number-average molecular weight of phenoxy resin is 40000~60000, relative to 100 parts of liquid epoxies, matter
Measuring number is 5~15 parts.Curing agent, relative to 100 parts of liquid epoxies, mass fraction is 1~5 part.
Preferably, aromatic amine curing agent is diaminodiphenyl-methane, diaminodiphenylsulfone, one in diaminodiphenyl ether
Kind is several.
Preferably, bimaleimide resin is diphenyl methane dimaleimide, diphenyl sulphone (DPS) bismaleimide, hexichol
One or more of ether bismaleimide.
Preferably, liquid epoxies is bis-phenol A glycidyl ether, Bisphenol F glycidol ether, bisphenol-A D glycidol
One or more of ether, novolac epoxy resin, cycloaliphatic epoxy resin.
Preferably, latent curing system master batch group is divided into dicyandiamide, modified dicyandiamine, carbamide derivative, imidazole derivatives
One or more of object, relative to 100 parts of liquid epoxies, mass fraction is 5~15 parts.
The beneficial effects of the present invention are: the addition of bi-maleimide modified aromatic amine curing agent introduces benzene in structure
Ring and imide ring structure, the crosslink density for improving resin system increase its modulus.Phenoxy resin is thermoplastic epoxy resin,
Fully compatible with matrix epoxy resin, the toughness of resin matrix is promoted after addition, and the viscosity that can widen resin is bent
Line solves the problems, such as that resin gummosis is serious when composite molding.The present invention, which can synchronize, improves the rigidity of epoxy resin and tough
Property, resin matrix and the modulus and breaking strain of carbon fiber are matched, are conducive to improve high mould carbon in composite material
The performance efficiency of fibre strength.
Specific embodiment
More detailed description is done to the present invention below by way of specific embodiment:
Embodiment 1
Aromatic amine curing agent is reacted into 5h according to the molar ratio of 2:1 with bimaleimide resin at 120 DEG C, preparation changes
Property aromatic amine curing agent, then by 5 number average molecular weights be 40000 phenoxy resin 100 parts of liquid epoxies are dissolved at 120 DEG C
In resin, 1 part of above-mentioned curing agent pre-polymerization 0.5h is then added, is cooled to 70 DEG C of additions, 5 parts of latent curing bodies
It is that masterbatch component is uniformly mixed, prepares activeness and quietness middle-temperature solidifying epoxy pre-dipping material resin system；By above-mentioned resin system in 130
Solidify 2 hours at DEG C, survey its stretch modulus be 3050MPa, elongation at break 2.54, bending modulus 3070MPa.It will be above-mentioned
Resin system prepares glue film using adhesive film machine, then via compounding machine and reinforcing fiber or fabric is compound prepares prepreg.It will be upper
It states prepreg to solidify 2 hours at 130 DEG C, surveying its interlaminar shear strength is 68MPa.
Embodiment 2
Aromatic amine curing agent is reacted into 2.5h at 140 DEG C according to the molar ratio of 3:1 with bimaleimide resin, is prepared
Curing agent, then the phenoxy resin that 10 number average molecular weights are 50000 is dissolved in 100 parts of liquid at 130 DEG C
In epoxy resin, 3 parts of above-mentioned curing agent pre-polymerization 1h are then added, are cooled to 75 DEG C of additions, 10 parts of latent curings
System master batch component is uniformly mixed, and prepares activeness and quietness middle-temperature solidifying epoxy pre-dipping material resin system；By above-mentioned resin system in
Solidify 2 hours at 130 DEG C, survey its stretch modulus be 3210MPa, elongation at break 2.75, bending modulus 3200MPa.It will
Above-mentioned resin system prepares glue film using adhesive film machine, then via compounding machine and reinforcing fiber or fabric is compound prepares prepreg.
Above-mentioned prepreg is solidified 2 hours at 130 DEG C, surveying its interlaminar shear strength is 71MPa.
Embodiment 3
Aromatic amine curing agent is reacted into 0.5h at 160 DEG C according to the molar ratio of 4:1 with bimaleimide resin, is prepared
Curing agent, then the phenoxy resin that 15 number average molecular weights are 60000 is dissolved in 100 parts of liquid at 150 DEG C
In epoxy resin, 5 parts of above-mentioned curing agent pre-polymerization 1.5h are then added, it is solid to be cooled to 80 DEG C of additions, 15 parts of latencys
Change system master batch component to be uniformly mixed, prepares activeness and quietness middle-temperature solidifying epoxy pre-dipping material resin system；By above-mentioned resin system
Solidify 2 hours at 130 DEG C, survey its stretch modulus be 3380MPa, elongation at break 2.89, bending modulus 3400MPa.
Above-mentioned resin system is prepared into glue film using adhesive film machine, is then presoaked via compounding machine and reinforcing fiber or the compound preparation of fabric
Material.Above-mentioned prepreg is solidified 2 hours at 130 DEG C, surveying its interlaminar shear strength is 73MPa.
Comparative example 1
The phenoxy resin that 5 number average molecular weights are 40000 is dissolved in 100 parts of liquid epoxies at 120 DEG C, is dropped
Temperature is added 5 parts of latent curing system master batch components to 70 DEG C and is uniformly mixed, and prepares activeness and quietness middle-temperature solidifying epoxy pre-dipping material
Resin system；Above-mentioned resin system is solidified 2 hours at 130 DEG C, surveys that its stretch modulus is 2830MPa, elongation at break is
2.45, bending modulus 2810MPa.Above-mentioned resin system is prepared into glue film using adhesive film machine, then via compounding machine and enhancing
Fiber or fabric is compound prepares prepreg.Above-mentioned prepreg is solidified 2 hours at 130 DEG C, surveying its interlaminar shear strength is
62MPa。
Claims (5)
1. a kind of preparation method of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems, it is characterized in that including following step
It is rapid:
(1) by aromatic amine curing agent and bimaleimide resin according to (2~4): the pre-polymerization at 120~160 DEG C of 1 molar ratio
0.5h~5h is reacted, curing agent is prepared；
(2) phenoxy resin is dissolved in liquid epoxies at 120~150 DEG C, is then added in the step (1) and obtains
Curing agent 0.5~1.5h of pre-polymerization, then to be cooled to 70~80 DEG C of addition latent curing system master batch components mixed
It closes uniformly, prepares activeness and quietness middle-temperature solidifying epoxy pre-dipping material resin system；The number-average molecular weight of the phenoxy resin is 40000
~60000, relative to 100 parts of liquid epoxies, mass fraction is 5~15 parts；The curing agent, relatively
In 100 parts of liquid epoxies, mass fraction is 1~5 part.
2. the preparation method of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems according to claim 1,
It is characterized in that the aromatic amine curing agent is diaminodiphenyl-methane, diaminodiphenylsulfone, one in diaminodiphenyl ether
Kind is several.
3. the preparation method of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems according to claim 1,
It is characterized in that the bimaleimide resin is diphenyl methane dimaleimide, diphenyl sulphone (DPS) bismaleimide, hexichol
One or more of ether bismaleimide.
4. the preparation method of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems according to claim 1,
Be characterized in that the liquid epoxies be bis-phenol A glycidyl ether, Bisphenol F glycidol ether, bisphenol-A D glycidol ether,
One or more of novolac epoxy resin, cycloaliphatic epoxy resin.
5. the preparation method of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems according to claim 1,
It is characterized in that the latent curing system master batch group is divided into dicyandiamide, modified dicyandiamine, carbamide derivative, imdazole derivatives
One or more of, relative to 100 parts of liquid epoxies, mass fraction is 5~15 parts.
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| CN201611121723.2A CN106751503B (en) | 2016-12-08 | 2016-12-08 | The preparation method of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems |
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| CN106751503B true CN106751503B (en) | 2019-01-22 |
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| KR102547854B1 (en) * | 2018-05-04 | 2023-06-26 | 삼성디스플레이 주식회사 | Foldable display device and method of manufacturing foldable display device |
| CN111564243B (en) * | 2018-12-27 | 2021-10-29 | 广西纵览线缆集团有限公司 | Heat-resistant aluminum alloy conductor |
| CN110343365B (en) * | 2019-07-04 | 2022-03-18 | 建滔(广州)高新材料有限公司 | High CTI epoxy resin for copper-clad plate and preparation method thereof |
| CN116144139B (en) * | 2023-01-03 | 2024-04-16 | 哈尔滨工程大学 | Resin for ship composite material and preparation method thereof |
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| CN103833958A (en) * | 2014-03-11 | 2014-06-04 | 吴江固德电材***股份有限公司 | Preparation method of environment-friendly single-component solvent-free epoxy impregnating resin |
| CN104945885A (en) * | 2015-07-14 | 2015-09-30 | 江苏兆鋆新材料股份有限公司 | Preparing method of epoxy resin carbon fiber prepreg |
| CN105385105A (en) * | 2015-11-17 | 2016-03-09 | 西安元创化工科技股份有限公司 | Bismaleimide modified epoxy resin as well as preparation method and application of bismaleimide modified epoxy resin |
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- 2016-12-08 CN CN201611121723.2A patent/CN106751503B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833958A (en) * | 2014-03-11 | 2014-06-04 | 吴江固德电材***股份有限公司 | Preparation method of environment-friendly single-component solvent-free epoxy impregnating resin |
| CN104945885A (en) * | 2015-07-14 | 2015-09-30 | 江苏兆鋆新材料股份有限公司 | Preparing method of epoxy resin carbon fiber prepreg |
| CN105385105A (en) * | 2015-11-17 | 2016-03-09 | 西安元创化工科技股份有限公司 | Bismaleimide modified epoxy resin as well as preparation method and application of bismaleimide modified epoxy resin |
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Effective date of registration: 20220627 Address after: 264211 Room 802, carbon fiber industrial park, caomiaozi Town, Lingang Economic and Technological Development Zone, Weihai City, Shandong Province Patentee after: Shandong Guangxuan New Material Co.,Ltd. Address before: A315, Changzhou science and technology building, Beijing University of chemical technology, No. 801, Changwu Middle Road, Wujin District, Changzhou City, Jiangsu Province, 213164 Patentee before: CHANGZHOU INSTITUTE OF ADVANCED MATERIAL OF BEIJING University OF CHEMICAL TECHNOLOGY |
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